A discrete octahedrally shaped [Ag₆]⁴⁺cluster encapsulated within silicotungstate ligands

Abstract

By the reaction of TBA(4)H(4)[γ-SiW(10)O(36)] (TBA = tetra-n-butylammonium) with AgOAc (OAc = acetate) using dimethylphenylsilane as a reductant in acetone, a unique polyoxometalate containing a discrete octahedrally shaped [Ag(6)](4+) cluster, TBA(8)[Ag(6)(γ-H(2)SiW(10)O(36))(2)]·5H(2)O, could be synthesized, and the molecular structure was determined.

Atomically Precise Multimetallic Semiconductive Nanoclusters with Optical Limiting Effects

“…As shown inFigure 2a,A g1ÀAg1 distances are 2.6901(18) and 2.7346(18) ,w hile the Ag1 À Ag2 distances are 2.7669(12) and 2.7755(19) ,r espectively.A ll of these values are clearly shorter than the Ag À Ag distance (ca. 2.889 )ofbulk Ag metal and the sum of the van der Waals radii of silver atoms (3.44 ), indicating the existence of strong AgÀAg bonding and closed-shell interactions.M eanwhile,t he AgÀAg distances in PTC-47 are comparable to those of reported [Ag 6 ] 4+ units (2.70-2.86 ), but shorter than those of [Ag 6 ] 6+ (2.81-3.28 ) [37,38]. Therefore,t he silver cluster in PTC-47 should also be [Ag 6 ] 4+ with delocalized electrons.T he presence of subvalent silver atoms can further be confirmed by its similar X-ray photoelectron spectrum as the former [Ag 8 ] 6+ and [Ag 22 ] 12+ containing silver clusters reported by Zheng et al (…”

Atomically Precise Multimetallic Semiconductive Nanoclusters with Optical Limiting Effects

“…2.889 Å) of bulk Ag metal and the sum of the van der Waals radii of silver atoms (3.44 Å), indicating the existence of strong Ag−Ag bonding and closed‐shell interactions. Meanwhile, the Ag−Ag distances in PTC‐47 are comparable to those of reported [Ag 6 ] 4+ units (2.70–2.86 Å), but shorter than those of [Ag 6 ] 6+ (2.81–3.28 Å) . Therefore, the silver cluster in PTC‐47 should also be [Ag 6 ] 4+ with delocalized electrons.…”

Octahedral and Cyclic [Ag6] Cluster Cores Stabilized by {Ag3(Spz)3(N‐triphos)3} Motifs [HSpz = Pyrazine‐2‐thiolate, N‐triphos = Tris((diphenylphosphanyl)methyl)amine]: Ag···Ag Interactions

“…There are a few examples of silver clusters containing octahedral [Ag 6 ] cluster core, such as [Ag 6 ] 0 in [Ag 34 (CO 3 ) 12 Cl 4 (dppm) 12 ],13 [Ag 6 ] 4+ in TBA 8 [Ag 6 (γ‐H 2 SiW 10 O 36 ) 2 ]14 and [Ag 14 (SC 6 H 3 F 2 ) 12 (PPh 3 ) 8 ],5 [Ag 6 @Ag 8 ] 4+ in [Ag 62 S 12 (SBu t ) 32 ] 2+ ,8 and a [Ag 12 ] 8+ clustering core in [Ag 12 (CF 3 CO 2 ) 14 ] 6– ,15 which contains two octahedral [Ag 6 ] cores sharing one edge. These so‐called subvalent cluster cores, also defined as superatom clusters, have delocalized free valence electrons which could enhance the stability of cluster core and tune the luminescent properties of clusters 16.…”